DE19935592A1 - Imidochrome compounds in catalyst systems for olefin polymerization - Google Patents

Abstract

The present invention relates to catalyst system containing at least one imidochrome compound and at least one activation compound. This invention also relates to imidochrome compounds, to a method for olefin polymerisation and to methods for producing said imidochrome compounds.

Description

The present invention relates to catalyst systems which contain imidochrome compounds, new imidochrome complexes, a process for the polymerization of olefins, and process for the production of imidochrome complexes.

Many of the catalysts used to polymerize α-olefins are based on immobilized chromium oxides (see e.g. Kirk-Othmer, "Encyclopedia of Chemical Technology", 1981, Vol. 16, p. 402). These result in i. a. Ethylene homo- and High molecular weight copolymers, however, are relatively un sensitive to hydrogen and therefore do not allow easy che molecular weight control. In contrast, can be Use of bis (cyclopentadienyl) - (US 3,709,853), Bis (indenyl) - or bis (fluorenyl) chromium (US 4,015,059), the an inorganic, oxidic carrier, the molecule Lar weight of polyethylene simply by adding hydrogen Taxes.

As with the Ziegler-Natta systems, you are also with the Chromver recently started looking for catalyst systems a uniformly defined, active center, so-called Sin gle-site catalysts. Through targeted variation of the ligand framework Activity, copolymerization behavior of the catalytic converter tors and the properties of the polymers obtained in this way are simple can be changed.

The representation of bis (tert.butylimido) bis (trimethylsiloxy) chromium by reacting dioxochrome dichloride with tert. butyl (tri methylsilyl) amine was described by W. Nugent et al. in Inorg. Chem. 1980, 19, 777-779. Diaryl derivatives of this compound Bis (tert.butylimido) di (aryl) chromium were described by G. Wilkinson et al. in J. Chem. Soc. Dalt. Trans. 1988, 53-60. The ent speaking dialkyl complexes were first described by C. Schaverien et al. (Organomet. 9 (1990), 774-782). You could too a monoimidochrome compound tert.butylimido (oxo) chromium dichloride by reaction of tert-butylimido-bis (trimethylsilano Isolate lato) oxochrome with phosphorus pentachloride (W. Nugent, In org. Chem. 1983, 22, 965-969).  

EP-A-641804 describes the use of bis (alkylimido) - and Bis (arylimido) chromium (VI) complexes for the polymerization of Olefins. In EP-A-816384 these bis (imido) chromium (VI) com plexes supported on polyaminostyrene for the polymerization of Ethylene and copolymerization of ethylene with higher α-olefins used. The representation of the bis (arylimido) chromium dichloride is here a three-stage synthesis route, since the implementation of Dio xochrome dichloride with N-trimethylsilylanilines not to bis (aryli mido) chromium dichloride leads.

G. Wilkinson et al. could tert.butylimidochrome (V) trichloride and represent its donor-coordinated derivatives (J. Chem. Soc. Dalt. Trans. 1991, 2051-2061).

The object of the present invention was to create new ones To find catalyst systems that could be easily modified sen and are suitable for the polymerization of α-olefins.

The task also consisted of an improved synthesis way to display bis (imido) chromium (VI) compounds to fin the.

Accordingly, catalyst systems have been found containing

• A) at least one imidochrome compound, obtainable by a process which comprises the following process steps:
  • a) contacting a dioxochrome compound with an N-sulfinyl compound R ¹ -N = S = O or R ² -N = S = O, in which the variables have the following meaning:
    R ¹ C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkyl aryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, the organic Radical R ^{1 can} also carry inert substituents, SiR ³ ₃ ,
    R ² R ³ C = NR ⁴ , R ³ C = O, R ³ C = O (OR ⁴ ), R ³ C = S, (R ³ ) ₂ P = O, (OR ³ ) ₂ P = O, SO ₂ R ³ , R ³ R ⁴ C = N, NR ³ R ⁴ or BR ³ R ⁴ ,
    R ³ , R ⁴ independently of one another are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical Hydrogen, if it is bound to a carbon atom, where the organic radicals R ³ and R ^{4 can} also carry inert substituents,
  • b) contacting the reaction product thus obtained with chlorine if a sulfinyl compound R ¹ -N = S = O was used and in the event that an N-sulfinyl compound R ² -N = S = O was used, with chlorine or sulfuryl chloride or with no other reagent,
• B) at least one activator compound and
• C) optionally one or more more for the polymer sation of olefins conventional catalysts.

Imidochrome compounds of the general formula II,

found, in which the variables have the following meaning:
R ² R ³ C = NR ⁴ , R ³ C = O, R ³ C = O (OR ⁴ ), R ³ C = S, (R ³ ) ₂ P = O, (OR ³ ) ₂ P = O, SO ₂ R ³ , R ³ R ⁴ C = N, NR ³ R ⁴ or BR ³ R ⁴ ,
X independently of one another fluorine, chlorine, bromine, iodine, NR ⁵ R ⁶ , NP (R ⁵ ) ₃ , OR ⁵ , OSi (R ⁵ ) ₃ , SO ₃ R ⁵ , OC (O) R ⁵ , β-diketonate, sulfate , Dicarboxylates, dialcoholates, BF ₄ ^- , PF ₆ ^- , or bulky weakly or non-coordinating anions,
R ³ -R ⁶ independently of one another are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical Hydrogen, if it is bound to a carbon atom, where the organic radicals R ³ to R ^{6 can} also carry inert substituents,
m 1 for Dianionic X, 2 for monoanionic X.

Imidochrome compounds of the general formula III

found, in which the variables have the following meaning:
R ² R ³ C = NR ⁴ , R ³ C = O, R ³ C = O (OR ⁴ ), R ³ C = S, (R ³ ) ₂ P = O, (OR ³ ) ₂ P = O, SO ₂ R ³ , R ³ R ⁴ C = N, NR ³ R ⁴ or BR ³ R ⁴ ,
X independently of one another fluorine, chlorine, bromine, iodine, NR ⁵ R ⁶ , NP (R ⁵ ) ₃ , OR ⁵ , OSi (R ⁵ ) ₃ , SO ₃ R ⁵ , OC (O) R ⁵ , β-diketonate, sulfate , Dicarboxylates, dialcoholates, BF ₄ ^- , PF ₆ ^- , or bulky weakly or non-coordinating anions,
R ³ -R ⁶ independently of one another are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical Hydrogen, if it is bound to a carbon atom, where the organic radicals R ³ to R ^{6 can} also carry inert substituents,
m 1 for Dianionic X, 2 for monoanionic X
L neutral donor,
n 0 to 3.

We have also found a process for preparing an imido chromium compound of the general formula IV

where the variables have the following meaning:
R ¹ C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, the organic Radical R ^{1 can} also carry inert substituents, SiR ³ ₃ ,
Z independently of one another are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, fluorine, chlorine , Bromine, iodine, NR ⁵ R ⁶ , NP (R ⁵ ) ₃ , OR ⁵ , OSi (R ⁵ ) ₃ , SO ₃ R ⁵ , OC (O) R ⁵ , β-diketonate, sulfate, dicarboxylates, dialcoholates, BF ₄ ^- , PF ₆ ^- , or bulky weakly or non-coordinating anions,
R ³ , R ⁵ , R ⁶ independently of one another are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C- Atoms in the aryl radical, hydrogen, if this is bonded to a carbon atom, where the organic radicals R ³ , R ⁵ and R ^{6 can} also carry inert substituents,
p 1 for dianionic Z, 2 for monoanionic Z,
characterized in that a dioxochrome compound is reacted with an N-sulfinyl compound R ¹ -NSO.

Furthermore, a process for the preparation of an imidochrome compound of the general formula I was found

where the variables have the following meaning:
X independently of one another fluorine, chlorine, bromine, iodine, NR ⁵ R ⁶ , NP (R ⁵ ) ₃ , OR ⁵ , OSi (R ⁵ ) ₃ , SO ₃ R ⁵ , OC (O) R ⁵ , β-diketonate, sulfate , Dicarboxylates, dialcoholates, BF ₄ ^- , PF ₆ ^- , or bulky weakly or non-coordinating anions,
R ¹ C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, the organic Radical R ^{1 can} also carry inert substituents, SiR ³ ₃ ,
R ³ , R ⁵ , R ⁶ independently of one another are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C- Atoms in the aryl radical, hydrogen, if this is bonded to a carbon atom, where the organic radicals R ³ , R ⁵ and R ^{6 can} also carry inert substituents,
L neutral donor,
n 0 to 3,
m 1 for Dianionic X, 2 for monoanionic X
characterized in that an imidochrome compound of the general formula V

where the variables have the following meaning:
R ¹ C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, the organic Radical R ^{1 can} also carry inert substituents, SiR ³ ₃ ,
X independently of one another fluorine, chlorine, bromine, iodine, NR ⁵ R ⁶ , NP (R ⁵ ) ₃ , OR ⁵ , OSi (R ⁵ ) ₃ , SO ₃ R ⁵ , OC (O) R ⁵ , β-diketonate, sulfate , Dicarboxylates, dialcoholates, BF ₄ ^- , PF ₆ ^- , or bulky weakly or non-coordinating anions,
R ³ , R ⁵ , R ⁶ independently of one another are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C- Atoms in the aryl radical, hydrogen, if this is bonded to a carbon atom, where the organic radicals R ³ , R ⁵ and R ^{6 can} also carry inert substituents,
m 1 for Dianionic X, 2 for monoanionic X,
reacted with chlorine.

A process for the preparation of an imidochrome compound of the general formula III was also found,

R ² R ³ C = NR ⁴ , R ³ C = O, R ³ C = O (OR ⁴ ), R ³ C = S, (R ³ ) ₂ P = O, (OR ³ ) ₂ P = O, SO ₂ R ³ , R ³ R ⁴ C = N, NR ³ R ⁴ or BR ³ R ⁴ ,
X independently of one another fluorine, chlorine, bromine, iodine, NR ⁵ R ⁶ , NP (R ⁵ ) ₃ , OR ⁵ , OSi (R ⁵ ) ₃ , SO ₃ R ⁵ , OC (O) R ⁵ , β-diketonate, sulfate , Dicarboxylates, dialcoholates, BF ₄ ^- , PF ₆ ^- , or bulky weakly or non-coordinating anions,
R ^3- R ⁶ independently of one another C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical Hydrogen, if it is bound to a carbon atom, where the organic radicals R ³ to R ^{6 can} also carry inert substituents,
L neutral donor,
n 0 to 3,
m 1 for Dianionic X, 2 for monoanionic X,
characterized in that a dioxochrome compound is reacted with an N-sulfinyl compound R ² -N = S = O in the presence of chlorine or sulfuryl chloride.

A process for the preparation of an imidochrome compound of the general formula VI was also found

where the variables have the following meaning:
R ² R ³ C = NR ⁴ , R ³ C = O, R ³ C = O (OR ⁴ ), R ³ C = S, (R ³ ) ₂ P = O, (OR ³ ) ₂ P = O, SO ₂ R ³ , R ³ R ⁴ C = N, NR ³ R ⁴ or BR ³ R ⁴ ,
Z independently of one another are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, fluorine, chlorine , Bromine, iodine, NR ⁵ R ⁶ , NP (R ⁵ ) ₃ , OR ⁵ , OSi (R ⁵ ) ₃ , SO ₃ R ⁵ , OC (O) R ⁵ , β-diketonate, sulfate, dicarboxylates, dialcoholates, BF ₄ ^- , PF ₆ ^- , or bulky weakly or non-coordinating anions,
R ³ -R ⁶ independently of one another are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical Hydrogen, if it is bound to a carbon atom, where the organic radicals R ³ to R ^{6 can} also carry inert substituents,
p 1 for dianionic Z, 2 for monoanionic Z,
characterized in that a dioxochrome compound is reacted with an N-sulfinyl compound R ² -NSO.

Furthermore, a process for the polymerization of olefins at temperatures in the range of 0 to 300 ° C and at pressures of 1 up to 4000 bar found, characterized in that the Polymerization in the presence of an inventive Performs catalyst system.

The process for producing the chromium complexes can use a wide variety of dioxochrome compounds as starting materials. The presence of the two oxo groups is important. Other ligands in the chromium starting compound can include the mono- and dianionic ligands listed for X and Z. Monoanioni cal ligands are e.g. B. halogens such. B. fluorine, chlorine, bromine and iodine, amides, e.g. B. dimethylamide, diethylamide and pyrrollidine, alcoholate, e.g. B. methanolate, ethanolate, isopropanolate, butanolate, phenolate and biphenolate, carboxylate, e.g. B. acetate and trifluoroacetate, β-diketonate, e.g. B. acetylacetonate, dibenzoyl methanate, 1,1,1-trifluoropentanedionate and 1,1,1,5,5,5, -hexafluoropentanedio nate, sulfonate, e.g. B. toluenesulfonate and trifluoromethanesulfonate, C ₁ -C ₂₀ alkyl, in particular C ₁ -C ₂₀ alkylsilyles, such as. B. methylene trimethylsilyl, bistrimethylsilylmethyl, C ₆ -C ₂₀ aryl, such as. B. mesityl or weak, or non-coordinating anions. Dianio African ligands are such. B. sulfate and chelating dicarboxy latex, such as. B. oxalate, fumarate, malonate or succinate and dialcoholates such. B. Glycolate. One or more mono- or dianionic ligands can be bound to the dioxochrome compound (see also Compr. Coord. Chem. Vol. 3, G. Wilkinson, Pergamon Press 1987, First Edition, chap. 35.6.1.3. S. 935 and chap. 35.7.1.-35.7.2. P. 938-941). In addition, one or more neutral donors L can also be coordinated to the chromium starting materials. The donor molecules usually have a heteroatom of the 15th or 16th group of the periodic table. Amines, e.g. B. trimethylamine, dimethylamine, N, N-dimethylaniline or pyridine, ether, e.g. B. tetrahydrofuran, diethyl ether, dibutyl ether, dimethoxyethane or dimethyldiethylene glycol, thioether, e.g. B. dimethyl sulfide, esters such as. B. methyl acetate, ethyl acetate or ethyl formate, ketones, for. As acetone, benzophenone or acrolein, Schiff bases, α-diimines, phosphines, such as. As trimethylphosphine, triethylphosphine or triphenylphosphine, phosphites such as. As trimethyl phosphite or triethyl phosphite, phosphine oxides, phosphoric acid esters or amides, such as. B. hexa methylphosphorsäuretriamid or N-oxides. The chromium compounds used can exist in a wide variety of oxidation states, preferably from +4 to +6 and very particularly preferably in the oxidation state +6. Preferred dioxochrome compounds are dioxochrome dihalides and dioxochromium dichloride is very particularly preferred.

The N-sulfinyl compounds used are for R ¹ -N = S = O z. B. N-sulfinylamines and for R ² -N = S = O z. B. N-sulfinyl carbamidines, N-sulfinyl carbamides, N-sulfinyl carbamates, N-sulfinyl carboxy amides, N-sulfinyl thiocarboxylamides, N-sulfinyl phosphonamides or N-sulfinyl sulfonamides. The N-sulfinyl compounds are usually prepared without problems and generally with a high yield from compounds containing NH ₂ groups and sulfinylating agents such as thionyl chloride, sulfur dioxide or with the aid of other N-sulfinyl compounds (Z. Chem. 22, (1982), 237- 245).

The radicals R ³ and R ⁴ are C ₁ -C ₂₀ alkyl, where the alkyl can be linear or branched, such as. B. methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, n-hexyl, n-hep tyl, n-octyl, n-nonyl, n -Decyl or n-dodecyl, 5- to 7-membered cycloalkyl, which in turn can carry a C ₆ -C ₁₀ aryl group as a substituent, such as. B. cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane or cyclododecane, C ₂ -C ₂₀ alkenyl, where the alkenyl can be linear, cyclic or branched and the double bond can be internal or terminal, such as. B. vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C ₆ -C ₂₀ aryl, where the aryl radical may be substituted by further alkyl groups, such as z. B. phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5-, or 2,6-dimethylphenyl, 2,3,4-, 2nd , 3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphenyl, or aryl alkyl, where the arylalkyl can be substituted by further alkyl groups, such as B. benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, where optionally two R ³ to R ^{4 may be connected} to form a 5- or 6-membered ring and / or inert substituents such as halogens , such as B. carry fluorine, chlorine or bromine. R ³ and R ⁴ are preferably hydrogen (if this is bonded to a carbon atom), methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, n- Hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, orto or para substituted alkyl or chloro, or bromo-substituted phenyls, ortho, ortho or ortho, para dialkyl- or dichloro, or dibromo-substituted phenyls, trialkyl - or trichloro-substituted phenyls, fluorine-substituted phenyls, naphthyl, biphenyl and anthranyl. Particularly preferred radicals R ³ and R ⁴ are methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl , Allyl, benzyl, phenyl, 2-chlorophenyl, 2-methylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,4-dichlorophenyl, 2,6 -Dibromophenyl, 2,4-dibromophenyl, 2,4,6-trimethylphenyl, 2,4,6-trichlorophenyl and pentafluorophenyl.

The radical R ¹ can be a C-organic radical, as described above for R ³ and R ⁴ , or an Si-organic radical. In the organosilicon substituents SiR ³ _3, where appropriate, two R ³ membered-6 to form a 5- or ring can be connected and the three radicals R ³ are independently selected such. B. tri methylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl. Particularly suitable Si organic substituents are trialkylsilyl groups with 1 to 10 carbon atoms in the alkyl radical, in particular trimethylsilyl groups. Preferred radical R ¹ is methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, n-he xyl, n-heptyl, n-octyl, vinyl, Allyl, benzyl, phenyl, orto or para substituted alkyl or chloro, or bromo-substituted phenyls, ortho, ortho or ortho, para dialkyl- or dichloro, or dibromo-substituted phenyls, trialkyl- or trichloro-substituted phenyls, fluorine-substituted phenyls, naphthyl, biphenyl and anthranyl. A particularly preferred radical R ¹ is benzyl, phenyl, 2-chlorophenyl, 2-methylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,4-dichlorophenyl, 2, 6-dibromophenyl, 2,4-dibromophenyl, 2,4,6-trimethylphenyl, 2,4,6-trichlorophenyl, pentafluorophenyl, naphthyl and anthranyl.

R ² can be an imino, isocyanide, formyl, oxo, thioxo, alkoxy carbonyl, aryloxycarbonyl, carbamoyl, phosphinoyl, dialkoxy or aryloxyphosphoryl, sulfonyl, dialkyl or arylino or dialkyl , or -arylboryl group. Preferred groups are sulfonyl and oxo, especially arylsulfonyls, such as. B. toluenesulfonyl, benzenesulfonyl, p-trifluoromethylbenzenesulfonyl or 2,6-diisopropylbenzenesulfonyl and aryloxo, such as. B. benzoyl, 2-methylbenzoyl, 2,6-dimethylbenzoyl, 2,6-diisopropylbenzoyl and 2,4,6-trimethylbenzoyl.

Imidochrome compounds are both mono- and Bisimidochromverbindungen.

The reaction to prepare the imidochrome compound (A) is shown in usually under an inert gas atmosphere, with z. B. nitrogen or Ar gon performed as an inert gas. Reaction step a) can at Tem temperatures between 0 to 150 ° C, preferably between 10 and 100 ° C. be performed. As a solvent find above all aprotic solvents use such as ether, e.g. B. Tetrahydro furan, diethyl ether, dibutyl ether, 1,2-dimethoxyethane or Diethylene glycol dimethyl ether, alkanes, e.g. B. pentane, n-hexane, iso- Hexane, n-heptane, n-octane, cyclohexane or decalin, aromatics, e.g. B. Benzene, toluene or xylene or chlorinated hydrocarbons such as Methylene chloride, chloroform, carbon tetrachloride or dichlor ethane. Mixtures of solvents can also be used. before alkanes and / or chlorinated hydrocarbons are added used and very particularly preferably n-octane and / or tetra chlorine-carbon.

The reaction product from step a) can be subjected to the second reaction step either with or without intermediate purification or isolation. The two reaction steps can also be carried out simultaneously in one step. The imidochrome complex with R ¹ is preferably isolated from reaction step a) before step b). For imidochrome complexes with R ² , step b) is optional. The R ² imidochrome complex can therefore also be mixed directly with the activator without being contacted with chlorine or sulfuryl chloride and used in the polymerization. However, the reaction products from a) with R ² can also be contacted with chlorine or sulfuryl chloride and only then mixed with the activator compound. For R ^2, steps a) and b) are preferably carried out simultaneously as a one-pot reaction.

The ratio of the dioxochrome compound to the N-sulfinyl compound lies between 1: 1 and 1: 10. Preferably between 1: 1 and 1: 3 and particularly preferably between 1: 1 and 1: 2.5.

The ratio of the dioxochrome compound to the N-sulfinyl compound lies between 1: 1 and 1: 10. Preferably between 1: 1 and 1: 3 and particularly preferably between 1: 1 and 1: 2.5.

Reaction step b) can be carried out in analogy to the procedure by G. Wilkinson et al. J. Chem. Soc. Dalt. Trans. 1991, 2051-2061 are carried out using the reaction product according to a) instead of bis (tert.butylimido) chromium dichloride. Sulfuryl chloride can also be used for R ² as chlorine transfer reagent. The sulfuryl chloride can be used in excess of the compound formed from step a). The ratio of sulfuryl chloride to the dioxochrome compound used can be between 1: 1 and 100: 1, preferably between 1: 1 and 10: 1 and particularly preferably between 1: 1 and 3: 1. The reaction is preferably carried out in carbon tetrachloride. The reaction temperature can be between 0 ° C and 100 ° C, preferably before it is between 10 ° C and 60 ° C and most preferably between 20 ° C and 60 ° C.

Catalyst systems in which imidochromium compounds of the general formula I are particularly preferred

where the variables have the following meaning:
X independently of one another fluorine, chlorine, bromine, iodine, NR ⁵ R ⁶ , NP (R ⁵ ) ₃ , OR ⁵ , OSi (R ⁵ ) ₃ , SO ₃ R ⁵ , OC (O) R ⁵ , β-diketonate, sulfate , Dicarboxylates, dialcoholates, BF ₄ ^- , PF ₆ ^- , or bulky weakly or non-coordinating anions,
R ¹ C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, the organic Radical R ^{1 can} also carry inert substituents, SiR ³ ₃ ,
R ³ , R ⁵ , R ⁶ independently of one another are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C- Atoms in the aryl radical, hydrogen, if this is bonded to a carbon atom, where the organic radicals R ³ , R ⁵ and R ^{6 can} also carry inert substituents,
L neutral donor,
n 0 to 3,
m 1 for Dianionic X, 2 for monoanionic X.

R ¹ and its preferred embodiments have already been described above. The description of the radicals R ³ , R ⁵ and R ⁶ is the same as for R ³ and R ^{4 described in} more detail above.

The substituents X result from the selection of the corresponding chromium starting compounds which are used for the synthesis of the chromium complexes. Suitable substituents X are, in particular, halogens such as fluorine, chlorine, bromine or iodine, and chlorine in particular. Trifluoroacetate, BF ₄ ^- , PF ₆ ^- and weakly or non-coordinating anions (see e.g. BS Strauss in Chem. Rev, 1993, 93, 927-942) such as B (C ₆ F ₅ ) ₄ ^- .

Amides, alcoholates, sulfonates, carboxylates and β-diketonates are also particularly suitable. By varying the radicals R ⁵ and R ^6, z. B. physical properties such as solubility are fine. Preferred are C ₁ -C ₁₀ alkyl such as methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and vinyl, allyl, benzyl and Phenyl used as radicals R ⁵ and R ⁶ . Some of these substituted ligands X are used with particular preference since they can be obtained from cheap and easily accessible starting materials. A particularly preferred embodiment is when X is dimethylamide, methanolate, ethanolate, isopropanolate, phenolate, naphtholate, tri-flat, p-toluenesulfonate, acetate or acetylacetonate. The dianionic ligands, as described in more detail above, can also be used. X is very particularly preferably chlorine and m is 2. The naming of the ligands X as anions does not specify what type of bond to the transition metal M is. If X is z. B. a non or weakly coordinating anion, the interaction between the metal M and the ligand X is rather electrostatic in nature. In the case of e.g. B. for X is alkyl, however, the bond is covalent. The various types of bindings are known to the person skilled in the art.

The donor L has also already been described above, where n is the Corresponds to the number of neutral donor molecules.  

The imidochrome compound I can be monomeric or dimer, but also po be lymer. If it is dimeric or polymeric, one or more Other ligands on the chromium - these can be X, L or the imido Being a group - bridging two chrome centers.

Preferred imidochrome complexes of the formula I and III are:

Methylimidochrome trichloride, ethylimidochrome trichloride, n-propyli midochrome trichloride, iso-propylimidochrome trichloride, n-butylimi chromium trichloride, isobutylimidochrome trichloride, tert-butylimi chromium trichloride, n-pentylimidochrome trichloride, n-hexylimido Rom trichloride, n-heptylimidochrome trichloride, n-octylimidochrome trichloride, allylimidochrome trichloride, benzylimidochrome trichlo rid, phenylimidochrome trichloride, naphthylimidochrome trichloride, Biphenylimidochrome trichloride, anthranylimidochrome trichloride, 2-chlorophenylimidochrome trichloride, 2-methylphenylimidochrome trichloride loride, 2,6-dimethylphenylimidochrome trichloride, 2,4-dimethylpheny limidochrome trichloride, 2,6-diisopropylphenylimidochrome trichloride, 2,6-dichlorophenylimidochrome trichloride, 2,4-dichlorophenylimidoch Rom trichloride, 2,6-dibromophenylimidochrome trichloride, 2,4-dibro mophenylimidochrome trichloride, 2,4,6-trimethylphenylimidochrome trichloride, 2,4,6-trichlorophenylimidochrome trichloride, pentafluo rophenylimidochrome trichloride, trifluoromethylsulfonylimidochrome trichloride, toluenesulfonylimidochrome trichloride, phenylsulfonyli midochrome trichloride, p-trifluoromethylphenylsulfonylimidochrome trichloride or 2,6-diisopropylphenylsulfonylimidochrome trichlo rid. Formylimidochrome trichloride, acylimidochrome trichloride, Ben zoylimidochrome trichloride, naphthoylimidochrome trichloride, Anthra noylimidochrome trichloride, 2-chlorobenzoylimidochrome trichloride, 2-methylbenzoylimidochrome trichloride, 2,6-dimethylbenzoylimido but Rom trichloride, 2,4-dimethylbenzoylimidochrome trichloride, 2,6-dii sopropylbenzoylimidochrome trichloride, 2,6-dichlorobenzoylimidoch Rome trichloride, 2,4-dichlorobenzoylimidochrome trichloride, 2,6-di bromobenzoylimidochrome trichloride, 2,4-dibromobenzoylimidochrome trichloride, 2,4,6-trimethylbenzoylimidochrome trichloride, 2,4,6-trichlorobenzoylimidochrome trichloride or pentafluorobenzoy limidochromtrichlorid.

The catalyst systems according to the invention further contain an activator, component (B), which is brought into contact with the chromium complex. Suitable activator compounds are, for example, those of the alumoxane type (or aluminoxane), in particular methylalumoxane MAO. Alumoxanes are e.g. B. by controlled addition of water or water-containing substances to alkyl aluminum compounds, in particular trimethyl aluminum, produced (z. B. US 4,404,344) Al co-catalyst suitable alumoxane preparations are commercially available. It is believed that this is a mixture of cyclic and linear compounds. The cyclic alumoxanes can be summarized by the formula (R ⁷ AlO) _s and the linear aluminoxanes by the formula R ⁷ (R ⁷ AlO) _s AlR ⁷ ₂ , where s indicates the degree of oligomerization and is a number from approximately 1 to 50. Advantageous alumoxanes essentially contain alumoxane oligomers with a degree of oligomerization of about 2 to 30 and R ⁷ is preferably a C ₁ -C ₆ alkyl and particularly preferably methyl, ethyl, butyl or isobutyl.

In addition to the alumoxanes, such can also be used as activator components be used, as in the so-called cationic Akti vation of the metallocene complexes are used. Such Ak tivator components are e.g. B. from EP-B-0468537 and from EP-B-0427697 known. In particular, as such activator compounds (B) boranes, boroxines or borates, such as. B. Trial kylborane, triarylborane, trimethylboroxine, dimethylanilinium traarylborate, trityltetraarylborate, dimethylaniliniumborataben zoles or tritylboratabenzenes (see WO-A-97/36937) are used become. Boranes or borates are particularly preferably used, which carry at least two perfluorinated aryl residues.

Also activator compounds with stronger oxidizing properties can be used, such as B. silver borates, especially silver tetra kispentafluorophenylborate or Ferroceniumborate, in particular Ferrocenium tetrakispentafluorophenylborate or Ferroceniumtetra phenyl borate.

Furthermore, compounds such as aluminum can be used as the activator component nium alkyls, especially trimethyl aluminum, triethyl aluminum, Triisobutylaluminium, Tributylaluminium, Dimethylaluminiumchlo rid, dimethyl aluminum fluoride, methyl aluminum dichloride, methyl aluminum sesquichloride, diethyl aluminum chloride or aluminum tri fluoride can be used. The hydrolysis products from Aluminum alkyls with alcohols can be used (see z. B. WO-A-95/10546).

Alkyl activators can also be used as activator compounds bindings of lithium, magnesium or zinc can be used like z. B. methylmagnesium chloride, methylmagnesium bromide, ethylmagnesi umchloride, ethylmagnesium bromide, butylmagnesium chloride, phenyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, methyl lithium, ethyl lithium, methyl zinc chloride, dime ethyl zinc or diethyl zinc.  

Catalyst systems in which the assets are particularly preferred gate connection (B) is selected from the following group: Aluminoxane, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, Me ethyl aluminum dichloride, ethyl aluminum chloride, methyl aluminum sesquichloride, dimethylanilinium tetrakispentafluorophenylborate, Trityltetrakispentafluorophenylborate or trispentafluorophenyl borane.

Sometimes it is desirable to have a combination of different ones To use activators. This is e.g. B. be in the metallocenes knows, in which boranes, boroxines (WO-A-93/16116) and borates often can be used in combination with an aluminum alkyl. Gene rell is also a combination of different activator compos possible with the chromium complexes according to the invention.

The amount of activator compounds to be used depends on the Type of activator. In general, the molar ratio Chromkom plex (A) to activator compound (B) from 1: 0.1 to 1: 10,000 gene, are preferred 1: 1 to 1: 2000. The molar ratio of Chromium complex (A) to dimethylanilinium tetrakispentafluorophenylbo rat, trityltetrakispentafluorophenylborate or trispentafluoro phenylborane is preferably between 1: 1 and 1:20, and especially preferably between 1: 1 and 1:10, preferred to methylaluminoxane between 1: 1 and 1: 2000 and particularly preferably between 1:10 and 1: 1000. Since many of the activators, such as. B. Aluminum alkyls who also used to remove catalyst poisons den (so-called scavenger), the amount used is also of depending on the purity of the other ingredients. The expert can, however, determine the optimal amount by simply trying men.

The mixture with the activator compound can differ in the Most aprotic solvents are used, alkanes are preferred such as pentane, hexane, heptane or octane or aromatics such as benzene, Toluene and xylene, pentane, hexane, heptane are particularly preferred and toluene. Also solvent mixtures, especially of alkanes with aromatics are inexpensive to get the solubility of To be able to adapt the catalyst system.

The mixture with the activator compound takes place at temperatures between -50 ° C and 150 ° C, preferably between 10 ° C and 50 ° C and very particularly preferably between 15 ° C and 30 ° C.

For polymerization, one or more of the Invention appropriate catalyst systems are used simultaneously. Thereby can e.g. B. bimodal products can be obtained. A wider pro  Duct spectrum can also by using the invention Imidochrome compounds in combination with another polyme risk-active catalyst (C) can be achieved. Here, min least one of the catalyst systems according to the invention in counter were at least one for the polymerization of olefins usual catalyst (C) used. As catalysts (C) preferred Ziegler Natta catalysts on the Titanium based, classic Phillips based catalysts of chromium oxides, metallocenes, the so-called constrained geome try complexes (see e.g. EP-A-416815 or EP-A-420436), nickel and Palladium bisimin systems (for their representation see WO-A-98/03559), iron and cobalt pyridinebisimine compounds (zu see WO-A-98/27124) or chromium pyrrole Compounds (see e.g. EP-A-608447) are used. So through such combinations z. B. bimodal products manufactured or be generated in situ comonomer. Depending on the cat gate selection one or more activators advantageous. The poly merization catalysts (C) can also be supported and simultaneously or in any order with the catalyst system according to the invention or its components con be clocked. Preactivation of the catalyst (C) with an activator connection (B) is possible.

The description and preferred embodiments of R ¹ to R ⁶ , as well as for X in the imidochrome compounds II and III, and also in the processes for the preparation of the chromium complexes I, III, IV and VI, the former using the imidochrome compound V, are the same as stated above. The reaction conditions are largely described above.

Z and its preferred embodiments are the same as for X described above and in addition also alkyls or aryls, particularly preferably methylenetrimethylsilyl, benzyl or mesityl.

The procedures for the preparation of chromium complexes III and V are principally carried out under the same conditions and the Reaction parameters are therefore jointly described below.

An essential reaction step is the contacting of the N-sulfonyl compound with the corresponding dioxochrome compound. The dioxochrome compounds have also been described above. The preferred dioxochrome compound is also dioxochromium dichloride. The N-sulfinyl compounds have also been described above. The preferred embodiments result from the preferred embodiments of the radicals R ¹ or R ^{2 of} the imido group of the chromium complex formed (see above). The reaction step has already been described in more detail for reaction step a). After that, a usual cleaning step z. B. by recrystallization or filtration.

The process according to the invention for the polymerization of olefins can with all technically known polymerization processes at temperatures in the range of 0 to 300 ° C and under pressure of Combine 1 to 4000 bar. The advantageous printing and Temperature ranges for performing the process depend accordingly strongly depends on the polymerization method. So they can be Catalyst systems used according to the invention in all known Polymerization process, for example in high-pressure poly merisation processes in tubular reactors or autoclaves, in Suspension polymerization process, in solution polymerization process or use in gas phase polymerization. Both High pressure polymerization process, usually at pressures between 1000 and 4000 bar, especially between 2000 and 3500 bar, are usually high butt Lymerisation temperatures set. Favorable temperature Ranges for these high-pressure polymerization processes lie between between 200 and 300 ° C, especially between 220 and 270 ° C. With never the pressure polymerization process is usually a Temperature set at least a few degrees below the Er softening temperature of the polymer is. The polymerization temperature can be between 0 ° C and 180 ° C. In particular, be in these polymerization processes temperatures between 50 and 180 ° C, preferably between 70 and 120 ° C, set. Of the According to the invention, the polymerization process mentioned is the gas phase polymerization, especially in gas phase fluidized bed re actuators, and suspension polymerization, especially in Loop and stirred tank reactors, as well as the solution poly merization particularly preferred. The gas phase polymerization can also in the so-called condensed, supercondensed or superkri table driving style. The different or same polymerization processes can also be used optionally be connected in series and thus a polymerization cas form kade. It can also be used to regulate the polymer properties also an additive such as B. hydrogen in the Polymerisationsver driving can be used.

Various olefinically unsaturated compounds can be polymerized by the process according to the invention, this also comprising the copolymerization. In contrast to some known iron and cobalt complexes, the transition metal complexes used according to the invention show good polymerization activity even with higher α-olefins, so that their suitability for copolymerization is particularly noteworthy. In addition to ethylene and α-olefins with 3 to 12 carbon atoms, the olefins also include internal olefins and non-conjugated and conjugated dienes such as butadiene, 1,5-hexadiene or 1,6-heptadiene, cyclic olefins such as cyclobutene, cyclopentene or norbornene and polar monomers such as Acrylic acid esters, acrolein, acrylonitrile, vinyl ethers, allyl ethers and vinyl acetate. Vinylaromatic compounds such as styrene can also be polymerized by the process according to the invention. At least one olefin selected from the group ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, cyclopentene and norbornene is preferably polymerized. A preferred embodiment of the process according to the invention is characterized in that mixtures of ethylene with C ₃ - to C ₈ -α-olefins are used as monomers.

The chromium complex can either be before or after contacting with the olefins to be polymerized with the activator (s) connections are brought into contact. Also a pre-activation with one or more activator compounds before mixing with the olefin and further addition of the same or different acti vator compounds after contacting this mixture with the Olefin is possible. Preactivation is usually done with Temperatures between 10-100 ° C, preferably between 20-80 ° C.

More than one of the catalyst systems according to the invention can also be used simultaneously in contact with the olefin to be polymerized be brought. This has the advantage that such a wide area Polymers can be generated. In this way, e.g. B. bimodal products are manufactured.

The catalyst systems according to the invention can optionally also be based on immobilized in an organic or inorganic carrier and in supported form can be used in the polymerization. This is a common method to avoid reactor deposits and the Control polymer morphology. As carrier materials are preferably silica gel, magnesium chloride, aluminum oxide, mesoporous Materials, aluminosilicates and organic polymers such as poly ethylene, polypropylene or polystyrene and especially silica gel or magnesium chloride used.

One or more of the catalyst systems according to the invention can be immobilized on a carrier. The components of the Catalyst systems can be used with the support in different rows follow or be brought into contact at the same time. This is in usually carried out in an inert solvent according to the immobilization can be filtered off or evaporated. Also is the use of the still moist, supported catalyst possible. So first the mixture of the carrier with the or Activator connections or first contacting the Trä  gers with the polymerization catalyst. Also a pre activation of the catalyst with one or more activators connections before mixing with the carrier is possible. The amount of chromium complex (A) in mmol per gram of carrier material can vary widely e.g. B. between 0.001 to 1 mmol / g. The before drawn amount of chromium complex (A) per gram of carrier material between 0.001 and 0.5 mmol / g, and particularly preferably between 0.005 and 0.1 mmol / g. In one possible embodiment, the Chromium complex (A) also in the presence of the carrier material be put. Another type of immobilization is that Prepolymerization of the catalyst system with or without previous To a support.

The process of the invention enables polymers of Represent olefins. The term polymerization, as used for loading Description of the invention used here includes both Polymerization as well as oligomerization, i.e. H. Oligomers and Polymers with molecular weights in the range of about 56 to 4000000 can be generated by these methods.

Due to their good mechanical properties, they are suitable Polyme produced with the catalyst system according to the invention Risks especially for the production of foils, fibers and form bodies.

The catalysts of the invention show moderate Productivities.

The comparative examples for the bimide chromium compounds described in EP-A-641 804 show that the monoimide compound (C ₆ F ₅ N) CrCl ₃ according to the invention gave higher activities. In the case of nor boron polymerization, the monoimido compounds did not produce any metathesis products in comparison with the bisimido compounds.

The new process for the preparation of bisimidochrome compounds is a one-pot synthesis. This allows up to two synthesis Steps in the representation of bis (arylimido) chromium complexes be saved.

N-sulfinylamines were used by S. Chenini and M. Pizzotti (Inorg. Chim. Acta 42, (1980), 65) for the synthesis of molybdenum imido compounds. It was suspected that the released SO ₂ would reduce the chromium species using the unstable chromium (VI) dioxo compounds. Surprisingly, however, this is not observed.

The following examples illustrate the invention:

Unless otherwise noted, all work was carried out in air and moisture exclusion. Toluene was over one Dried molecular sieve column or potassium / benzophenone and off distilled. Triethyl aluminum (2 M in heptane) and MAO (methyl aluminoxan 30% in toluene) were from Witco GmbH and Albemarle related.

analytics

Elemental analyzes were determined on a Heraeus CHN-Rapid.

IR spectra were recorded using a Nicolet 510M as a Nujol trituration recorded between KBr plates.

The η value was determined using an automatic Ubbelohde viscometer (Lauda PVS 1) with decalin as solvent at 130 ° C (ISO1628 at 130 ° C, 0.001 g / ml decalin).

EI mass spectra were recorded on a Varian MAT CH7.

Melting points were carried out on a melting point determination device B-540 from the Buechi company.

NMR spectra were recorded with a Bruker ARX 200 or Bruker AMX 300 added.

Abbreviations in the following tables:
Cat. Ex .: catalyst according to example
Yield: Yield polymer
gP: grams of polymer
Tg: glass temperature
Tm: melting temperature
h: Staudinger index (viscosity)
tBu: tert. butyl
Ts: para-toluenesulfone
Bz: benzoyl
Tf: trifluoromethanesulfone

example 1 Preparation of bis ((2,6-diisopropylphenyl) imido) chromium dichloride

A 0.84 molar solution of chromyl chloride in CCl ₄ (455 mg, 2.94 mmol CrO ₂ Cl ₂ ) was diluted with 30 ml octane and slowly added 1.45 g (6.47 mmol) (2,6-diispropylphenyl) sulfinylamine.

The reaction mixture was then refluxed for 12 hours, with an inert gas stream being passed through the reaction solution at times in order to drive off the SO _{2 formed} . The precipitated brown-violet solid was filtered off, washed with cold pentane and dried under high vacuum. Yield: 1.22 g (88%) of bis (diisopropylphenylimido) chromium dichloride.
1H-NMR (C ₆ D ₆ , 200 MHz): δ = 1.08 (d, 24H, 3J _HH = 6.8 Hz, CH (C H ₃ ) ₂ ), 3.86 (sept, 4H, 3J _HH = 6.7 Hz, C H (CH ₃ ) ₂ ), 6.72 (s, 6H, Ph- H ) ppm.
13 C-NMR (C ₆ D ₆ , 50 MHz): δ = 23.5 (CH ( C H ₃ ) ₂ ), 30.0 ( C H (CH ₃ ) ₂ ), 123.7 (Ph- C _(meta) ), 132.3 (Ph - C _(para) ), 148.9 (Ph- C _(ortho) ) ppm.
IR (Nujol): ~ = 2855 s, 1642 w, 1582 m, 1296 m, 1262 m, 1221 w, 1142 w, 1080 m (br), 1022 m (br), 912 w, 799 m, 754 w, 721 w, 563 m cm-1.
EI-MS: m / z = 175 (DipN +, 57%), 160 (Dip-H, 71%), 119 (C ₉ H ₁₂ +, 25%), 36 (Cl, 100%).
Dip = 2,6-diisopropylphenyl
Ph = phenyl

Example 2 Preparation of bis (tert.butylimido) chromium dichloride

A 0.84 molar solution of chromyl chloride in CCl ₄ (566 mg, 3.67 mmol CrO ₂ Cl ₂ ) was diluted with 20 ml octane and 963 mg (8.08 mmol) tert-butylsulfinylamine were added. The reaction mixture was then refluxed for 12 hours, an inert gas stream being passed through the reaction solution for some time in order to drive off the SO _{2 formed} . The precipitated violet solid was filtered off, washed with cold pentane and dried in a high vacuum. Yield: 770 mg (79%) bis (ter.butyl imido) chromium dichloride.
1H-NIR (CDCl ₃ , 200 MHz): δ = 1.60 (s, 18H, C (C H ₃ ) ₃ ) ppm.
13 C-NMR (CDCl ₃ , 50 MHz): δ = 30.2 (C ( C H ₃ ) ₃ ) ppm.

Example 3 Preparation of bis ((2,4,6-trimethylphenyl) imido) chromium dichloride

A 0.84 molar solution of chromyl chloride in CCl ₄ (605 mg, 3.92 mmol CrO ₂ Cl ₂ ) was diluted with 20 ml octane and slowly added 1.66 g (8.63 mmol) mesitylsulfinylamine. The reaction mixture was then heated to reflux for 12 hours, with an inert gas stream being passed through the reaction solution at times in order to drive off the SO _{2 formed} . The precipitated red-brown solid was filtered off, washed with cold pentane and dried in a high vacuum. Bis ((2,4,6-trimethylphenyl) imido) chromium dichloride was isolated in 91% yield.
1H-NMR (C ₆ D ₆ , 200 MHz): δ = 1.84 (s, 6H, Mes-C H _{3 (para)} ), 2.25 (s, 12H, Mes-C H _{3 (ortho)} ), 6.23 (s , 4H, Mes- H ( _meta) ) ppm.

Example 4 Preparation of bis (pentafluorophenylimido) chromium dichloride

A 0.84 molar solution of chromyl chloride in CCl ₄ (3.30 g; 21.4 mmol CrO ₂ Cl ₂ ) was diluted with 80 ml tetrachloromethane and 10.79 g (47.08 mmol) pentafluorophenylsul finylamine was added at room temperature. The reaction mixture was then stirred for 4 hours until gas evolution was no longer observed. When cooling, a gentle stream of inert gas was passed through the reaction solution in order to drive off the SO _{2 formed} during the reaction. The precipitated dark red solid was filtered off, washed with cold pentane and dried under high vacuum. Yield: 95% bis (pentafluorophenylimido) chromium dichloride.
19F-NMR (CDCl ₃ , 188 MHz): δ = -144.2 (d, 4F, 3J _FF = 15.3 Hz, Arf-F _(ortho) ), -148.3 (t, 2F, 3J _FF = 20.4 Hz, Art -F _(para) ), -155.9 (t, 4F, 3J _FF = 20.3 Hz, Art-F _(meta) ) ppm.
IR (Nujol): ~ = 1632 s, 1507 s, 1263 m, 1150 m, 1121 m, 1063 s, 997 s, 864 w, 802 w, 721 w, 642 m, 561 m, 440 w cm-1.
Arf = pentafluorophenyl

Example 5 Reaction of dioxochrome dichloride with N- (toluenesulfonyl) sulfiny lamid

A 0.84 molar solution of chromyl chloride in CCl ₄ was dissolved at room temperature with 2.2 equivalents of sulfinylamide in tetrachloromethane. The reaction mixture was then heated under reflux until gas evolution could no longer be observed. The resulting brown solid was filtered off, washed with pentane and dried in vacuo. Yield 90%.

Only a sharp signal was observed for the connection in the EPR spectrum.
Average values for elementary analysis:
C - 25.31 H - 2.37 N - 3.28 Cl - 22.89 S - 12.15 Cr - 13.16

Example 6 Reaction of dioxochrome dichloride with N- (toluenesulfonyl) sulfinyl amide in the presence of chlorine

A 0.84 molar solution of chromyl chloride in CCl ₄ was mixed with 2.2 equivalents of N- (toluenesufonyl) sulfinylamide in carbon tetrachloride at room temperature. A chlorine gas stream was passed through the reaction solution for 10 minutes. The reaction mixture was then heated at reflux until gas evolution could no longer be observed. A weak stream of chlorine gas was also passed through the reaction solution during the reaction. The resulting yellow-brown solid was filtered off, washed with pentane and dried in vacuo. The yield was about 90%.

Alternatively, 5 ml instead of chlorine gas can be added to the above solution Sulfuryl chloride can be added. After stirring for 24 hours The room temperature was worked up analogously.

Very broad, weak signals can be seen in the ¹ H-NMR spectrum, which indicate a paramagnetic connection.

Examples 7 to 9 Reaction of the bis (imido) chromium dichloride with chlorine (analogous to G. Wilkinson et al., J. Chem. Soc. Dalton Trans. 1991, 2051-2061)

These experiments were for complexes with the following residues on the imido ligands carried out: tert-butyl (7), 2,6-diisopropylphenyl (8) and pentafluorophenyl (9)

5 g of the bis (imido) chromium dichloride were dissolved in 50 ml of methylene chloride solved. A chlorine gas stream was at room temperature for 10 minutes passed through the reaction solution. Then one Hour at room temperature, then the volatile parts removed in vacuum.

These reactions were almost quantitative.

Elemental analysis

• 1. calculated: C 43.20, H 5.14, N 4.20,
  found: C 41.60, H 5.24, N 5.46.
• 2. calculated: C 21.23, N 4.13,
  found: C 21.27, N 4.25.

Example 10 ethylene polymerization

0.20 mmol of the chromium compound from Example 5 were obtained in 61 ml Toluene dissolved. The solution was placed in a 250 ml glass autoclave transferred, there first tempered to 0 ° C and then 30 min saturated with 3 bar ethene. Then the reaction was stopped by Zu administration of 670 mg of MAO (Cr: Al = 1:50) dissolved in 40 ml of toluene tet. The first polymer fell after only a few minutes particles from the reaction solution. After a response time The reaction was carried out for 3 hours by dropping the polymer tion mixture broken into a methanol / hydrochloric acid mixture. The the resulting polymer precipitate was filtered off with metha nol washed and dried at 100 ° C in a vacuum. 2.3 g poly Ethylene with a melting point of 136 ° C and η = 19 were obtained th.

Example 11 Norbornene ethene copolymerization

Initially, 0.200 mmol of the chromium compound from Example 5 were suspended in 50 ml of toluene. This solution was transferred to a 250 ml glass autoclave. 40 ml of a norbornene-toluene solution (318.60 mmol of norbornene) were then added to this solution. The reaction mixture obtained was first heated to 0 ° C. and then saturated with 3 bar ethene for 30 minutes. The reaction was then started by adding 1.34 g of MAO (Cr: Al = 1:50), dissolved in 20 ml of toluene. After a reaction time of 1.5 hours, the reaction was stopped by dropping the polymerization mixture into a methanol / hydrochloric acid mixture. The polymer precipitate obtained was filtered off, washed with methanol and dried at 70 ° C. in vacuo. 28 g of polymer with T _{g of} 128 ° C. could be obtained.

Example 12 Hexenpolymerisation

First, 0.106 mmol of the chromium compound from Example 5 were in 10 ml of toluene dissolved. 2.64 ml of 1-hexene were then added to this solution (21.24 mmol) was given. The reaction mixture obtained was on 25 ° C and the polymerization by adding 300 mg of MAO (Cr: Al = 1:50), dissolved in 3 ml of toluene. After a reak The polymerization time of 3 days was dropwise the polymerization mixture in a methanol / hydrochloric acid mixture Broken. This resulted in an oily, sticky precipitate that could not be filtered. Therefore, the methanol was back distilled off and the residue obtained in 50 ml of cyclohexane  added. This solution was then covered with 10 ml of water tet to wash the polymer obtained chromium-free. Subsequently the aqueous phase was separated. From the organic phase the solvent was distilled off in vacuo and the obtained Polymer residue was dried in vacuo. The yield was 3% polyhexene.

Examples 13 to 16 Norbornenpolymerisation

• A) Activation of the catalyst with a commercial MAO-To luol solution:
  First, 0.106 mmol of the chromium compound from Example 5 were mixed with 2 g of norbornene in 10 ml of toluene. The reaction mixture obtained was heated to 25 ° C. and the reaction was started by adding 3 ml of 1.53 M methylaluminoxane solution (in toluene). After a reaction time of one hour, the reaction was stopped by dropping the polymerization mixture into a methanol / hydrochloric acid mixture. The polymer precipitate obtained was filtered off, washed with methanol and dried in vacuo.
• B) Activation of the catalyst with solid MAO, which was taken up again in toluene.
  First, 0.106 mmol of the chromium compound from Example 5 were mixed with 2 g of norbornene, dissolved in 10 ml of toluene. The reaction mixture obtained was then heated to 25 ° C. and the reaction was started by adding 300 mg of MAO, dissolved in 3 ml of toluene. After a reaction time of one hour, the reaction was stopped by dropping the reaction mixture into a methanol / hydrochloric acid mixture. The polymer precipitate obtained was filtered off, washed with methanol and dried in vacuo.

The results of the polymerizations are shown in Table 1.

Comparative Examples 17 and 18 Norbornenpolymerisation

The experiments were carried out as before for norbornene polymerization B) described. In Example 17 the Chromver bond from Example 4, in Example 18 the chromium compound Example 2 used.  

The results of the polymerizations are shown in Table 1.  

Table 1

Results of norbornene polymerization

• a) metathesis, refers to product obtained by ring öff Metathesis Polymerization (ROMP) (determined by NMR Measurements and Tg values).

Examples 19 to 24 ethylene polymerization

There were 0.05 mmol of the chromium compound shown in Table 2 dissolved in 20 ml of toluene. The solution was poured into a 250 ml glass transferred to autoclaves, there first tempered to 60 ° C and on finally saturated with 3 bar ethene for 30 min. Then the reak tion by adding 12.5 mmol MAO (Cr: Al = 1: 250), dissolved in 20 ml Toluene, started. It fell after a few minutes out polymer particles from the reaction solution. After a reak tion time of 30 minutes at 60 ° C under constant ethylene pressure The reaction was set at 3 bar by dropping the polymer Mix in 400 ml of methanol / conc. Hydrochloric acid mixture (10: 1) canceled. The polymer precipitate obtained was reduced filtered, washed with methanol and dried at 100 ° C. in vacuo net.

Example 24 is shown for comparison.

Table 2

Results of ethylene polymerization

Examples 25-27 ethylene polymerization

400 ml of toluene were placed in an 11-autoclave at 70 ° C. then the amount of catalyst given in Table 3 became 2.5 ml a 30% MAO solution (12 mmol) suspended and after 10 Mi grooves introduced into the reactor. The polymerization was completed by Injection of 40 bar ethylene started. After an hour of poly merisation time at 40 bar ethylene and 70 ° C the reaction canceled by relaxing and the polymer as previously described ben worked up.

Table 3

Results of ethylene polymerization

Example 28 ethylene polymerization

The polymerization was as described for Ex. 25-27 carried out. The chromium complex from Example 9 was used. 2 ml of triethylaluminum (4 mmol) were introduced as cocatalyst puts.

14.5 g of polyethylene with an η value of 7.8 dl / g were possible will hold. The activity was 3 gP / mmol.bar.h.

Claims (14)

1. Containing catalyst systems

• A) at least one imidochrome compound, obtainable by a process which includes the following process steps:
  • a) contacting a dioxochrome compound with an N-sulfinyl compound R ¹ -N = S = O or R ² -N = S = O, in which the variables have the following meaning:
    R ^{1 is} C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, the organic Radical R ^{1 can} also carry inert substituents, SiR ³ ₃ ,
    R ² R ³ C = NR ⁴ , R ³ C = O, R ³ C = O (OR ⁴ ), R ³ C = S, (R ³ ) ₂ P = O, (OR ³ ) ₂ P = O, SO ₂ R ³ , R ³ R ⁴ C = N, NR ³ R ⁴ or BR ³ R ⁴ ,
    R ³ , R ⁴ independently of one another are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical , Hydrogen, if this is bound to a carbon atom, the organic radicals R ³ and R ⁴ also being able to carry inert substituents,
  • b) contacting the reaction product thus obtained with chlorine if a sulfinyl compound R ¹ -N = S = O was used and in the event that an N-sul finyl compound R ² -N = S = O was used, with chlorine or sulfuryl chloride or with no other reagent,
• B) at least one activator compound and
• C) if desired, one or more further catalysts customary for the polymerization of olefins.

2. A catalyst system according to claim 1, in which the imidochrome compound by contacting dioxochrome dichloride with the N-sulfinyl compound is available. 3. A catalyst system according to claim 1, in which Imidochromver compounds of the general formula I
are used, in which the variables have the following meaning:
X independently of one another fluorine, chlorine, bromine, iodine, NR ⁵ R ⁶ , NP (R ⁵ ) ₃ , OR ⁵ , OSi (R ⁵ ) ₃ , SO ₃ R ⁵ , OC (O) R ⁵ , β-dike tonate, sulfate, dicarboxylates, dialcoholates, BF ₄ ^- , PF ₆ ^- , or bulky weakly or non-coordinating anions,
R ¹ C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, the organic radical R ^{1 can} also carry inert substituents, SiR ³ ₃ ,
R ³ , R ⁵ , R ⁶ independently of one another are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6-20 C- Atoms in the aryl radical, hydrogen, if this is bonded to a carbon atom, where the organic radicals R ³ , R ⁵ and R ^{6 can} also carry inert substituents,
L neutral donor,
n 0 to 3,
m 1 for Dianionic X, 2 for monoanionic X 4. Catalyst system according to claims 1 to 3, characterized ge indicates that the activator compound (B) from the group Aluminoxane, trimethyl aluminum, triethyl aluminum, triiso butyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum chloride, Me ethyl aluminum sesquichloride, dimethylanilinium tetrakispenta fluorophenylborate, trityltetrakispentafluorophenylborate or Trispentafluorophenylborane is selected.   5. Imidochrome compound of the general formula II
where the variables have the following meaning:
R ² R ³ C = NR ⁴ , R ³ C = O, R ³ C = O (OR ⁴ ), R ³ C = S, (R ³ ) ₂ P = O, (OR ³ ) ₂ P = O, SO ₂ R ³ , R ³ R ⁴ C = N, NR ³ R ⁴ or BR ³ R ⁴ ,
X independently of one another fluorine, chlorine, bromine, iodine, NR ⁵ R ⁶ , NP (R ⁵ ) ₃ , OR ⁵ , OSi (R ⁵ ) ₃ , SO ₃ R ⁵ , OC (O) R ⁵ , β-dike tonate, Sulfate, dicarboxylates, dialcoholates, BF ₄ ^- , PF ₆ ^- , or bulky weakly or non-coordinating anions,
R ³ -R ⁶ independently of one another are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical , Hydrogen, if it is bound to a carbon atom, where the organic radicals R ³ to R ^{6 can} also carry inert substituents,
m 1 for Dianionic X, 2 for monoanionic X 6. Imidochrome compound of the general formula III
where the variables have the following meaning:
R ² R ³ C = NR ⁴ , R ³ C = O, R ³ C = O (OR ⁴ ), R ³ C = S, (R ³ ) ₂ P = O, (OR ³ ) ₂ P = O, SO ₂ R ³ , R ³ R ⁴ C = N, NR ³ R ⁴ or BR ³ R ⁴ ,
X independently of one another fluorine, chlorine, bromine, iodine, NR ⁵ R ⁶ , NP (R ⁵ ) ₃ , OR ⁵ , OSi (R ⁵ ) ₃ , SO ₃ R ⁵ , OC (O) R ⁵ , β-dike tonate, Sulfate, dicarboxylates, dialcoholates, BF ₄ ^- , PF ₆ ^- , or bulky weakly or non-coordinating anions,
R ³ -R ⁶ independently of one another are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical , Hydrogen, if it is bound to a carbon atom, where the organic radicals R ³ to R ^{6 can} also carry inert substituents,
L neutral donor,
n 0 to 3,
m 1 for Dianionic X, 2 for monoanionic X 7. Process for the preparation of an imidochrome compound of the general formula IV,
wherein the variables have the meaning given in claim 3 and:
Z independently of one another are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, fluorine, chlorine , Bromine, iodine, NR ⁵ R ⁶ , NP (R ⁵ ) ₃ , OR ⁵ , OSi (R ⁵ ) ₃ , SO ₃ R ⁵ , OC (O) R ⁵ , β-diketonate, sulfate, dicarboxylates, dialcoholates, BF ₄ ^- , PF ₆ ^- , or bulky weakly or non-coordinating anions,
p 1 for dianionic Z, 2 for monoanionic Z,
characterized in that a dioxochrome compound is reacted with an N-sulfinyl compound R ¹ -NSO. 8. Process for the preparation of an imidochrome compound of the general formula I
wherein the variables have the meaning given in claim 3:
characterized in that an imidochrome compound of the general formula V
wherein the variables have the meaning given in claim 3,
reacted with chlorine. 9. Process for the preparation of an imidochrome compound of the general formula III
wherein the variables have the meaning given in claim 6,
characterized in that a dioxochrome compound is reacted with an N-sulfinyl compound R ² -N = S = O in the presence of chlorine or sulfuryl chloride. 10. Process for the preparation of an imidochrome compound of the general formula VI
wherein the variables have the meaning given in claims 6 and 7,
characterized in that a dioxochrome compound is reacted with an N-sulfinyl compound R ² -NSO. 11. Process for the polymerization of olefins at temperatures in the Range from 0 to 300 ° C and at pressures from 1 to 4000 bar, characterized in that the polymerization in Presence of a catalyst system according to claims 1 to 4. 12. The method according to claim 11, characterized in that one polymerization in the gas phase, solution or suspension leads.   13. The method according to claim 11 or 12, characterized in that at least one olefin selected from the group ethene, Propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, cyclo pentene and norbornene is polymerized. 14. The method according to claims 11 to 13, characterized records that at least one catalyst system according to the An say 1 to 4 immobilized on a carrier.